Thiazolyl monoazo dyes containing the imidoethylsulfonylethyl group



3,515,714 THIAZOLYL MONOAZO DYES CONTAINING THE IMIDOETHYLSULFONYLETHYL GROUP John I. Dale III, and Max A. Weaver, Kingsport, Tenn., assignors to Eastman Kodak Company, Rochester, N.Y., a corporation of New Jersey No Drawing. Filed July 22, 1966, Ser. No. 567,048 Int. Cl. C09b 29/36; D06p 1/02 U.S. Cl. 260-158 7 Claims ABSTRACT OF THE DISCLOSURE Water-insoluble thiazolyl-azo-aniline compounds in which the nitrogen atom of the aniline coupling component is substituted by a dicarboximidoethyl-sulfonyethyl group are useful as dyes for hydrophobic textile materials.

This invention relates to novel water-insoluble azo compounds and, particularly, to thiazolylazo dyes for hydrophobic textile fibers, yarns and fabrics.

The novel azo compounds of the invention are characterized by the general formula R represents a thiazolyl radical, e.g. a radical having the structure:

wherein X represents the various substituents that can be present on the thiazolyl ring, representative examples of which are hydrogen; alkyl, e.g. methyl, ethyl; substituted alkyl such as halogenoalkyl, e.g. chloromethyl, trifluoromethyl, cyanoalkyl, e.g. cyanoethyl, nitroalkyl, e.g. nitroethyl, hydroxyalkyl, e.g. hydroxyethyl; alkoxyl, e.g. methoxyl; acylamido, e.g. acetamido; nitro; halogeno, e.g. chloro, bromo; cyano; alkylsulfonyl, e.g. methylsulfonyl, substituted alkoxyl, e.g. halogenoalkoxy; substituted alkylsulfonyl, e.g. cyanoethylsulfonyl; carbamoyl; N-alkylcarbamoyl, e.g. N,N-dimethylcarbamoyl; phenyl; benzyl; benzoyl; benzamido; benzylarnino; N-alkylbenzylamino; N-alkylarylamino, e.g. N-methylphenylamino; alkoxycarbonyl, e.g. ethoxycarbonyl; hydroxyl; acyl, e.g. acetyl; formyl; sulfamoyl; N-alkylsulfamoyl, e.g. N-ethylsulfamoyl; alkylsulfonamido, e.g. methylsulfonamido, ethylsulfonarnido; substituted alkylsulfonamido, e.g. cyanoethylsulfonamido, dicarboxylic acid imido, e.g. succinimido; thiocyanato; alkylthio, e.g. methylthio; benzoyl; combinations thereof; and m represents 1 or 2.

R represents a monocyclic carbocyclic aromatic group of the benzene series having the structure wherein Y represents the substituents present on the phenylene ring, illustrative examples of which are hydrogen, alkyl, e.g. methyl, ethyl; substituted alkyl such as halogenoalkyl, e.g. chloromethyl, cyanoalkyl, e.g. cyanoethyl, nitroalkyl, e.g. nitroethyl, hydroxyalkyl, e.g. hydroxyethyl; alkoxyl, e.g. methoxyl; substituted alkoxyl, e.g., cyanoethoxyl; acylamido, e.g. acetamido; halogeno, e.g. chloro, bromo; phenyl; phenylalkyl, e.g. benzyl; benzamido; benzylamino: N-alkylarylamino, e.g. N-methylphenylamino, hydroxyl, alkylsulfonamido, e.g. methylsulfonamido, ethylsulfonamido; substituted alkylsulfonted States Patent "Ice amido, e.g. chloroethylsulfonamido; dicarboxylic acid imido, e.g. succinimido; thiocyanato; alkylthio, e.g. meth= glthio; benzoyl; combinations thereof; and n represents 1,

R represents hydrogen or an alkyl radical, preferably lower alkyl, i.e. from 1 to 4 carbon atoms, being nonsubstituted or substituted such as hydroxyalkyl, e.g. hydroxyethyl, polyhydroxyalkyl, e.g. 2,3-dihydroxypropyl, alkoxyalkyl, e.g. methoxyethyl, cyanoalkyl, e.g. cyanoethyl, cyanoalkoxyalkyl, e.g. B-cyanoethoxyethyl, acyloxyalkyl, e.g. acetoxyethyl, alkoxycarbonylalkyl, e.g. ethoxycarbonylethyl, halogenalkyl, e.g. chloroethyl, a-chloropropyl, bromoethyl, hydroxyhalogenoalkyl, e.g. 3-chloro- Z-hydroxypropyl, alkylsulfonylalkyl, e.g. methylsulfonylethyl, alkyl-OCOOCH CH e.g.

CHgOCOOCHz-CHF e.g. carbamoylalkyl, e.g. carbamoylethyl, dicarboxylic acid imidoalkyl, e.g. succinimidoethyl, phthalimidoethyl; benzyl; phenoxyalkyl, e.g. fl-phenoxyethyl; alkylsulfonamidoalkyl, e.g. methylsulfonamidoethyl; N-alkylcarbamoylalkyl, e.g. N-ethylcarbamoylethyl; dicarboxamidoalkyl, e.g. fl-dicarboximidoethyl; e.g. carbamatoalkyl, e.g. carbamatoethyl; and the like; or R represents a monocyclic carbocyclic aromatic radical of the benzene series, e.g. nonsubstituted phenyl and substituted phenyl such as represented by the monovalent analog of R above, e.g. alkylphenyl, alkoxyphenyl, nitrophenyl, alkylsulfonylphenyl, etc. A preferred group represented by R includes hydrogen, alkyl, alkoxyalkyl, phenoxyalkyl, acyloxyalkyl, haloalkyl, hydroxyalkyl, ethoxycarbonylalkyl, carbamoylalkyl, alkylsulfonylalkyl or cyanoalkyl, the alkyl groups of which are lower alkyl;

R represents a dicarboximido group, i.e. a dicarboxylic acid imido group having the structure:

wherein Z represents a hydrocarbon radical or group of carbon atoms necessary to complete a ring, preferably a ring containing 4 or 5 carbon atoms in addition to the imido nitrogen atom, i.e. the hydrocarbon residue of the dicarboxylic acid anhydride from which the radical is derived. The divalent hydrocarbon group can be a straight or branched chain, saturated or unsaturated divalent aliphatic group such as alkylene, e.g. ethylene, pentamethyh ene, isopropylene, isobutylene; alkenylene, e.g., vinylene (-CH=CH-), which can be substituted with various groups such as those present on the alkyl groups represented by R above, for example, halo, e.g. chloro, bromo, hydroxy, nitro, cyano, acyloxy, e.g. acetoxy, etc. The divalent hydrocarbon group represented by Z can also be a divalent carbocyclic group such as the monoand bi-cyclic aromatic groups and the monoand bi-cyclic non-aromatic groups, examples of which are o-phenylene, 1,8-naphthylene, 2-cyclohexylene, bicyclo[2.2.l]-5-heptenylene, etc. Like the aliphatic hydrocarbon groups, the divalent ca'rbocyclic groups can be substituted with many groups such as, for example, those represented by X in relation to the definition of R above. The more preferred groups represented by Z are an alkylene group of 2. to about 4 carbon atoms and a phenylene group.

Upon reading the following examples further describing and illustrating the invention, it will be apparent that numerous variations in the substituents represented by X and Y and those on the groups represented by R and R can be made without materially affecting the dye affinity of the compounds of the invention. As can be seen from the examples given below, the substituents attached to the groups represented by R, R R and R serve primarily as auxochrome groups to control the color of the azo compound and, thus, are not critical. The alkyl groups represented by X, Y and R can consist of many carbon atoms in a straight or branched chain, e.g. dodecyl, 3- ethylhexyl. However, for reasons of economy and avail-= ability, the preferred alkyl groups are lower alkyl, i.e. up to about four carbon atoms. For similar reasons, the alkyl moiety of the various substituents that can be present on the groups represented by R, R R and R are preferably carbon chains of up to about four carbon atoms. As used herein, the term acyl refers to the residue of a carboxylic acid having the formula ACO wherein A is an aliphatic or carbocyclic group.

The novel azo dyes of the invention, characterized by Formula I above, are prepared by coupling a conventional diazonium salt of an aminothiazole compound having the structure:

NH2 s with a coupling component having the structure:

R2 R bi- CzHtSO20215114-11 (III Thus, the schematic reaction is illustrated as follows:

The coupling components represented by structure (111) above, are prepared by the reaction of an alkylor an aryl-dicarboxylic acid imide with a vinylsulfonylethylaniline derivative, the reaction being schematically illustrated as follows: I

The preparation of the coupling components and the dyes produced therefrom will be more fully illustrated by the following examples.

PREPARATION OF THE CQUPLERS N=2= (Z-succinimido ethyl sulfonyl) ethyl-N-ethyl-m toluidine N-2- Z-phthalimido ethylsulfonyl) ethyl-N-ethyl im toluidine In accordance with the above procedure, phthalimide is reacted with Nfivinylsulfonylethyl-N -ethyl-m-toluidine to obtain the coupler having the structure:

N-ethyl-N-Z- (2-phthalimidoethylsulfonyl) ethyl-m-= chloroaniline In accordance with the above procedure, phthalimide is reacted with N-B-vinylsulfonylethyl-N-ethyl-rn-chloro= aniline to obtain the coupler having the structure:

Preparation of the dyes EXAMPLE 1 An amount of 2.90 g. of Z-amino-S-nitrothiazole is dissolved at room temperature in 25 ml. of water and 13.5 ml. cone. H 50 This solution was cooled to :'10

C. and 1.54 g. NaNO in 10 ml. H was added below 0 C. The solution is stirred 10 min. and added to a solu tion of 8.00 g. of N-2-(2-phthalimidoethylsulfonyl)ethyl- N ethyl-m-toluidine in ml. 1:5 acid (1 part propionic acid:5 parts acetic acid) at 5 C. After 30 min. the reaction mixture is drowned in water and the precipitated dye filtered, washed with water and air dried. The product dyes polyester fibers blue-violet shades of excellent sublimation fastness. The dye has the structure:

C i J CO OzN- N=N N CHzCHzSOzCHzCHzN 1 a EXAMPLE 2 added until a brown color on Congo Red paper is obtained and after 1 /2 hr. the reaction mixture is drowned in water. The precipitated dye is filtered, washed with water and air dried. It dyes polyester fibers and cellulose acetate red-violet shades and displays excellent sub= limation fastness on polyester fibers. The dye has the following structure:

l 1 /C 2H5 Br S )N=N- coon:

I CHzCHzSOzCHzCHzN H3 CO C H:

EXAMPLE 3 A diazonium solution is prepared from 2.90 g. of 2- amino-S-nitrothiazOle as in Example 1. This solution is added to 6, 56 g. of N-2-(2-succinimidoethylsulfonyl)ethyl aniline in '50 ml 1:5 acid. The dye is worked up as in the Example l. It gives violet shades on polyesters and cellulose acetate. The dyeings have excellent sublimation fastness on polyesters and good light fastness on both fibers.

It has the structure:

EXAMPLE 5 A diazoninm solution is prepared as in Example 1 from 2.90 g. of 2-amino-5-nitrothiazole. This solution is added to 8.40 of N-ethyl-N-Z-(2-phthalimidoethylsulfonyl)- ethyl-m-clgloroaniline in ml. 1:5 acid. The dye is worked as in Example 1. It dyes polyester and cellulose acetate fifiers a violetshade having good light fastness and good sublimation fastness on polyesters. It has the structure:

The thiazolylazo compounds set forth in the following table arel prepared according to the procedure described in the above Examples. The appropriate aminothiazole compounds of Formula II are diazotized and coupled with the coupler compounds of Formula III to yield the compounds 0t Formula I. The color of thecompounds refers to dyeings on polyester fibers.

TABLE Example X R R2 Z .Color 6 5-NO2 m-Tolylene -02H4CN CH2 Violet.

7 5-N0z -d0 C zCH2C /(CH2)3 Do.

8 5-NO2 ...-.d0 CH2CH2OCH3 --CHOH Do.

9 5-NOz .d0 CH2CH2OCOCH3 ?HOCOOH D0.

C 0 CH 10 5-NOz do CHzCH2N l Do.

l1 5-NO2 ..do -CH2CH2CO2C2H5 Do.

12 5-N0z ."do --CH2CH2B1 13 5-N02 ..-do CH2OH2SO2CH3 -OHCH D0.

- HCHa 14 5-NO2 do CH2CH2CONH2 (lJHC1 Do.

--CH2 5NO2 ..-do -CHCH2N CHCH3 CO CH: 16 5NO2 do CH2CH2 C0NH A Do.

. HCN

TABLEContinued Example X R R2 Z Color 17 --N0g ...--do 421120112011 t Do.

18 4-01; Phenylene C2Hr Red.

19 4-0111; m-OCH;phenylene- C2Hs Red.

20 4-COzC2H o-Chlorophenylene H Red.

21 4-NHCOGH3 m-Chlorophenylene -C2H5 Red.

22 None 2-OCHa-5-NHCOCHa C2Ha Same as above..- Redphenylene. violet. 23 4-GH3-5-COCH; 2-0CH3-5-GHa-phenylene- CiHs do Red. 24 5-CN 2,5-dl-OCHa-pheny1ene--.- 02H5 do Bed. 25 5-SCN 2-0OH;-5-Clphenylene.... -C2Hs Red.

26 5-SO2CH; .d0 -C2Hs Same as above... Red. 27 4-phenyl d0 C2H5 Red.

28 4-CH;-5-SCN --Cz s Same as above"... Red. 29 4-CHs-5-NO2 ..-..do --O2Hs d0 Violet.

The azo compounds of the invention can be used for dyeing textile materials, including protein and synthetic polymer fibers, yarns and fabrics, giving a variety of fast brilliant red to violet shades when applied thereto by con ventional dye methods. The azo compounds have high affinity for cellulose ester, polyester, and nylon fibers. When the compounds are used for dyeing such hydrophobic materials, they should be free of water-solubilizing groups such as suite and carbonyl. In general, the dyes have excellent fastness, for example, to light, washing, gas (atmospheric fumes) and sublimation. The dyes are especially sublimation resistant on polyesters.

As described above, the present azo compounds have the characteristic structure of Formula I. This distinctive structure imparts unexpected properties to the compounds, including the above-described light fastness and sublimation resistance. Thus, We have found the compounds of the in vention to possess excellent properties when used as dyes on hydrophobic textile materials, especially polyester, when tested by methods such as described in the A.A.T.C. Technical Manual, 1965 edition.

The compounds of the invention can be used for dyeing hydrophobic fibers such as linear polyester, cellulose ester, acrylic, polyamide, etc., fibers in the manner described in US. Pats. 2,880,050, 2,757,064, 2,782,187 and 2,043,827. The following example illustrates a method by which the azo compounds of the invention can be used to dye polyester textile materials.

0.1 g. of the dye is dissolved in the dye pot by warming in 5 cc. of ethylene glycol monomethyl ether. A 2% sodium-N-methyl-N-oleyl taurate and 0.5% sodium lignin sulfnate aqueous solution is added, with stirring, until a fine emulsion is obtained. Water is then slowly added to a total volume of 200 cc. Then, 3 cc. of Dacronyx (a chlorinated benzene emulsion) are added and 10 grams of a textile fabric made of Kodel polyester fibers are'entered. The fabric is worked 10, minutes without heat and then for IO-minutes at C. The dye bath is then brought to the boil and held at the boil for one hour. Following this, the fabric is rinsed in Warm water, thenscoured in aqueous 0.2% soap, 0.2% soda ash solution. After scouring, the fabric is rinsed with water and dried. Accordingly, since the compounds of the invention .are water-insoluble, they can be applied from aqueous dispersions in the manner-0f the so-called dispersed dye. However, coloration can. also be effected, for example, by incorporating the com-.

pounds into the spinning dope and spinning the fiber as usual.

The compounds of the invention are not necessarily equivalents when used as dyes. The degree of dye affinity and fastness properties vary to some degree, for example,

depending upon the material being dyed and the formula of the azo compound. Thus, for example, all the: compounds will not have the same degree of dye affinity for the same material. For example, the substituents X, Y and R serve primarily as auxochrome groups to control the color of the azo compound.

Polymeric linear polyester materials of the terephthalate type are illustrative of the linear aromatic polyester textile materias that can be dyed with the new azo compounds of our invention. The terephthalate fibers sold under the trademarks Kodel, Dacron, and Terylene, for example, are illustrative of the polyester textile materials that can be dyed. Kodel polyester fibers are more partciularly described in US. Pat. 2,901,446. Dacron and T'je'rylene polyester fibers are described, for example, in (LS. fPat. 2,465,319. The polymeric linear polyester materials disclosed in US. Pats. 2,945,010, 2,957,745 and 2,9,89,363 for example, can be dyed. The linear aromatic polyester materials specifically named have a melting point of at least 200 C. 5

Nylon, in fiber, yarn and fabric form, is representative of polya'mides which can be dyed with the azo compounds.

We claim: 7

1. A water-insoluble compound having the formula X is hydrogen, lower alkyl, lower alkoxy, acetyl, f ormyl, acetamido, nitro, chlorine, bromine, trifiuoromethyl, cyano, lower alkylsulfonyl, carbamoyl, phenyl, benzyl, benzamido, lower alkoxycarbonyl, suliamoyl, lower alkylsulfonamido, thiocyanato, lower alkylthio, or benzoyl',

m is l or 2;

Y is hydrogen, lower alkyl, lower alkoxyl, chlorine, bromine, acetamido, lower alkylsulfonamido, or benzamido;

n is 1 or 2;

R is hydrogen; lower alkyl; lower alkyl substituted with hydroxy, lower alkoxy, cyano, acetoxy, lower alkoxycarbonyl, chlorine, bromine, lower alkylsulfonyl, carbamoyl, lower alkylcarbarnoyl, loweif'alkylsulfonarnido, phenoxy, succinimido, or phthalimido;

benz yl; phenyl; or 'phenyl substituted with lower alkyl, lower alkoxyl, chlorine, bromine, nitro, or lower alkylsulfonyl; and

Z is alkylene of 2 to 4 carbon atoms, hydroxyethylene, acetqxyethylene, chloroethylene, cyanoethylene,'vinylene,jo-phenylene, 1,8-naphthylene, 1,2-cyclhe1jgylene, 1,2-cyclopentylene, or bicyclo [2.2.11-5-hepter'1'ylene; andjwherein I lower. designates a carbon content of from 1 to 4 carbon atoms.

2. A compound defined in claim 1 wherein X is nitro, chlorine, bromine, cyano, trifiuoromethyl,

lower alkylsulfonyl, or lower alkoxycarbonyl;

m is 1;

Y is hydrogen, lower alkyl, lower alkoxy, chlorine,

bromine, or acetamido;

n is 1 or 2; and R is lower alkyl or lower alkyl substituted with lower alkoxy, phenoxy, aeetoxy, chlorine, bromine, hydroxy, ethoxyca' i'bonyl, carbamoyl, lower alkylsulfonyl, or cyano. 3. A compound a mula defined in claim 1 having the for- N CH l 2 oo OzN 8 N=N '"N CHnCHzSOzCHzCHzN 4. A compound as defined in claim 1 having the formula 6. A compound as defined in claim 1 having the formula CHzCHzSOzCHzCHzN Cz s COCHZ CO H:

7. A compound as defined in claim 1 having the formula CHARLES B. PARKER, Primary Examiner D. M. PAPUGA, Assistant Examiner US. Cl. X.R. 

